Macromolecular engineering using commodity monomers is becoming a major trend in polymer technology to satisfy the demand for new properties, improved cost effectiveness, ecology and quality. Functional polymers with low molecular weight, low polydispersity, compact, branched structures and terminally-located reactive groups are expected to exhibit superior performance/cost characteristics, by virtue of lower inherent viscosity and higher reactivity vs. conventional linear statistical copolymers.
The terminally-functional branched polymers appear to be ultimate reactive substrates for networks, because the branch points can substitute for a significant portion of expensive reactive groups and provide better distribution of the reactive groups. Polymers having large numbers of short branches below critical molecular weight are unlikely to form any entanglements and should exhibit low inherent viscosity and good flow even in concentrated solutions.
Conventional techniques for synthesizing well-defined branched polymers require expensive multistep processes involving isolation of reactive intermediate macromonomers. The macromonomers have polymerizable end groups, which are usually introduced using functional initiator, terminating or chain transfer agent. Well-defined branched polymers are prepared by the macromonomer homopolymerization or copolymerization with suitable low molecular weight comonomer selected based on known reactivity ratios. These methods have been reviewed and only single-branch polymers from single incorporation of the macromonomers are reported; multiple reincorporation of the growing macromonomers was never attempted, e.g., R. Milkovich, et al., U.S. Pat. No. 3,786,116; P. REMP, et al., Advan. Polymer Sci., 58, 1 (1984); J. C. Salamone, ed., Polymeric Materials Encyclopedia, Vol. 3 and 4 (1996).
Several linear macromonomers were prepared by end-capping of living anionic polyolefins with unsaturated terminating agents providing polymerizable olefin end-groups, e.g., R. Asami et al., Macromolecules, 16, 628 (1983). Certain macromonomers have been incorporated into simple graft polymers by homo- or copolymerization with branched structure not well-characterized and reincorporation of the macromonomers into more complex structures was not considered.
Dendrimers or hyperbranched polymers are conventionally prepared using expensive, special multifunctional monomers or expensive multistep methods requiring repetitive isolation of the reactive intermediates. Nothing in the prior art discloses synthetic conditions for production of macromonomers or polymers containing branches upon branches.